An optical polarization modulation technique was adapted to provide a simple, fast, and flexible method for studying the kinetics and growth characteristics of thin oxide layers, using Al2O3 as an example. The optical technique allows precise determination of the amount of remaining metallic Al as a function of the initial Al thickness, while scanning a laser spot across the wedge. Optical data suggest that the oxide growth rate for the ultrathin layers may be dependent on the specific microstructure. In situ x-ray photoelectron spectroscopy performed on homogenous samples confirmed the interpretation of the optical results. ©2000 American Institute of Physics.